Certain 3-(substituted thio)-2-benzoyl-cyclohex-2-enones

ABSTRACT

A compound of the formula ##STR1## wherein R is halogen, C 1  -C 2  alkyl, C 1  -C 2  alkoxy, nitro; cyano; C 1  -C 2  haloalkyl, or R a  SO n  -- wherein n is 0 or 2 and R a  is C 1  -C 2  alkyl; R 1  is hydrogen or C 1  -C 4  alkyl; R 2  is hydrogen or C 1  -C 4  alkyl; or R 1  and R 2  together are alkylene having 2 to 5 carbon atoms; R 3  is hydrogen or C 1  -C 4  alkyl; R 4  is hydrogen or C 1  -C 4  alkyl; or R 3  and R 4  can be oxo; R 5  is hydrogen or C 1  -C 4  alkyl; R 6  is hydrogen or C 1  -C 4  alkyl; or R 5  and R 6  together are alkylene having 2 to 5 carbon atoms; and R 7  and R 8  independently are (1) hydrogen; (2) halogen; (3) C 1  -C 4  alkyl; (4) C 1  -C 4  alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1  -C 4  haloalkyl; (9) R b  SO n  -- wherein n is the integer 0, 1 or 2; and R b  is (a) C 1  -C 4  alkyl; (b) C 1  -C 4  alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR c  R d  wherein R c  and R d  independently are hydrogen or C 1  -C 4  alkyl; (11) R e  C(O)-- wherein R e  is C 1  -C 4  alkyl or C 1  -C 4  alkoxy; (12) SO 2  NR c  R d  wherein R c  and R d  are as defined; or (13) --N(R c )C(O)R d  wherein R c  and R d  are as defined; m is the integer 0, 1 or 2; and R 9  is C 1  -C 4  alkyl, phenyl, cyano, substituted phenyl, or --(CH 2 ) x  --C(O)O-- (C 1  -C 4  alkyl) whrein X is the integer 1, 2 or 3.

DESCRIPTION OF THE INVENTION

This invention relates to 3-(substitutedthio)-2-benzoyl-cyclohex-2-enones and their use as herbicides.

One embodiment of this invention is an herbicidal composition comprisingan herbicidally active 3-(substituted thio)-2-benzoyl-cyclohex-2-enonesand an inert carrier therefor wherein the 2-position of the benzoylmoiety is substituted as herein recited and the 4-position preferably issubstituted with an electron withdrawing group, such as halogen, cyanoor trifluoromethyl. The 4-, 5- and 6-positions of the cyclohex-2-enonemoiety can be substituted, preferably with the groups hereinafterrecited. More preferably, the cyclohex-2-enone moiety has nosubstitution or the 4- or 6-position is substituted with two methylgroups. The 3-, 4- and 5-positions of the benzoyl moiety can besubstituted, preferably with the groups hereinafter recited.

Also embodied within the scope of this invention are novel compoundshaving the following structural formula ##STR2## wherein

R is halogen; C₁ -C₂ alkyl, preferably methyl; C₁ -C₂ alkoxy, preferablymethoxy; nitro; cyano; C₁ -C₂ haloalkyl, preferably trifluoromethyl; orR^(a) SO_(n) -- wherein n is 0 or 2, preferably 2 and R^(a) is C₁ -C₂alkyl, preferably methyl. Preferably, R is chlorine, bromine, C₁ -C₂alkyl, C₁ -C₂ alkoxy, cyano, nitro, C₁ -C₂ alkylthio or C₁ -C₂alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethylor methylsulfonyl;

R¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl, most preferably R¹ is hydrogen or methyl;

R² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl, most preferably R² is hydrogen or methyl; or

R¹ and R² together are alkylene having 2 to 5 carbon atoms;

R³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl; most preferably R³ is hydrogen or methyl;

R⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl; most preferably R⁴ is hydrogen or methyl; or

R³ and R⁴ together can be oxo;

R⁵ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl; most preferably R⁵ is hydrogen or methyl;

R⁶ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl, most preferably R⁶ is hydrogen; or

R⁵ and R⁶ together are alkylene having 2 to 5 carbon atoms;

R⁷ and R⁸ independently are (1) hydrogen; (2) halogen, preferablychlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4)C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7)nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b)SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferablychloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl; (10) --NR^(c) R^(d) wherein

R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e)C(O)-- wherein

R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) --SO₂ NR^(c) R^(d) whereinR^(c) and R^(d) are as defined; (13) --N(R^(c))C(O)R^(d) wherein R^(c)and R^(d) are as defined; and

m is the integer 0, 1 or 2, preferably 0 or 2, most preferably 2;

R⁹ is C₁ -C₄ alkyl, preferably methyl or ethyl; phenyl; substitutedphenyl; cyano; --(CH₂)_(x) C(O)O--(C₁ -C₄ alkyl) wherein x is theinteger 1, 2 or 3.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includeschlorine, bromine, iodine and fluorine. The term "C₁ -C₄ alkoxy"includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,isobutoxy and t-butoxy. The term "C₁ -C₄ haloalkyl" includes the alkylgroups defined above under C₁ -C₄ alkyl in which one or more hydrogen isreplaced by chloro, bromo, iodo or fluoro.

Preferably, R⁷ is in the 3-position. Most preferably R⁷ is hydrogen.Preferably R⁸ is in the 4-position. Most preferably R⁸ is halogen,cyano, trifluoromethyl, or R^(b) sO₂ wherein R^(b) is C₁ -C₄ alkyl,preferably methyl or C₁ -C₄ haloalkyl, preferably chloromethyl,difluoromethyl or trifluoromethyl.

The compounds of this invention are active herbicides of a general type.This is, they are herbicidally effective against a wide range of plantspecies. The method of controlling undesirable vegetation of the presentinvention comprises applying an herbicidally effective amount of theabove-described compounds to the area where control is desired.

The compounds of the present invention can be prepared by the followingtwo- or, if necessary, three-step general method. ##STR3## wherein Rthrough R⁸ are as defined.

Generally in step (a) the benzoyl dione is dissolved in an inert solventsuch as methylene dichloride and an excess, usually 150 to 200 molepercent, of oxalyl chloride is added followed by a catalytic amount (0.1equivalent) of dimethylformamide. The reaction mixture is stirred fromone hour to one day at room temperature. The reaction product isisolated using conventional techniques. ##STR4## wherein R through R⁹are as defined.

Generally, in step (b) the 3-chloro-2-benzoylcycloalkenone is dissolvedin an inert solvent such as tetrahydrofuran and the thiol (1.0 to 2.0equivalents) is added, followed by a base (1.0 to 2.0 equivalents) suchas triethylamine and the solution is stirred 1 to 8 hours at roomtemperature and the product is isolated using conventional techniques.

Alternatively in step (b), the thiol can be added as a thiolate,preferably the sodium thiolate. The product in step (b) can then beisolated using standard techniques. ##STR5## wherein R through R⁹ are asdefined, m is the integer 1 or 2 and [O] is an oxidizing agent,preferably peroxides such as peracetic acid.

Generally, in reaction step (c) the vinylsulfide is dissolved inmethylene chloride and an oxidizing agent such as m-chloroperoxybenzoicacid (1.1-2.2 equivalents) is added portion-wise and the reactionstirred for 1 to 8 hours. The product may be isolated using conventionaltechniques.

The precursor benzoyl diones used in step (a) can be prepared by thefollowing two-step general method.

The process proceeds via the production of an enol ester intermediate asshown in reaction (1). The final product is obtained by rearrangement ofthe enol ester as shown in reaction (2). The two reactions may beconducted as separate steps by isolation and recovery of the enol esterusing conventional techniques prior to conducting step (2), or byaddition of a cyanide source to the reaction medium after the formationof the enol ester, or in one step by inclusion of the cyanide source atthe start of reaction (1). ##STR6## wherein R through R⁸ are as definedand the moderate base is as defined, preferably tri-C₁ -C₆ alkylamine,alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the dione and substituted benzoylreactant are used, along with a mole amount or excess of the base. Thetwo reactants are combined in an organic solvent such as methylenechloride, toluene, ethyl acetate or dimethylformamide. The base orbenzoyl reactant preferably is added to the reaction mixture withcooling. The mixture is stirred at 0° C.-50° C. until the reaction issubstantially complete.

The reaction product is worked up by conventional techniques. ##STR7##wherein R through R⁸ are as defined.

Generally, in step (2) a mole of the enol ester intermediate is reactedwith 1 to 4 moles of the moderate base, preferably about 2 moles ofmoderate base and from 0.01 mole to about 0.5 mole or higher, preferablyabout 0.1 mole of the cyanide source (e.g., potassium cyanide or acetonecyanohydrin). The mixture is stirred in a reaction pot until therearrangement is substantially complete at a temperature below 80° C.,preferably about 20° C. to about 40° C., and the desired product isrecovered by conventional techniques.

The term "cyanide source" refers to a substance or substances whichunder the rearrangement conditions consists of or generates hydrogencyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of asource of cyanide anion and/or hydrogen cyanide, together with a molarexcess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium andpotassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4carbon atoms in the alkyl groups, such as acetone or methyl isobutylketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphaticaldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins;zinc cyanide; tri(lower alkyl)silyl cyanides, notably trimethyl silylcyanide; and hydrogen cyanide itself. Hydrogen cyanide is consideredmost advantageous as it produces relatively rapid reaction and isinexpensive. Among cyanohydrins the preferred cyanide source is acetonecyanohydrin.

The cyanide source is used in an amount up to about 50 mole percentbased on the enol ester. It may be used in as little as about 1 molepercent to produce an acceptable rate of reaction at about 40° C. on asmall scale. Larger scale reactions give more reproducible results withslightly higher catalyst levels of about 2 mole percent. Generally about1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enolester, of a moderate base. By the term "moderate base" is meant asubstance which acts as a base yet whose strength or activity as a baselies between that of strong bases such as hydroxides (which could causehydrolysis of the enol ester) and that of weak bases such asbicarbonates (which would not function effectively). Moderate basessuitable for use in this embodiment include both organic bases such astertiary amines and inorganic bases such as alkali metal carbonates andphosphates. Suitable tertiary amines include trialkylamines such astriethylamine. Suitable inorganic bases include potassium carbonate andtrisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per moleof enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularlypotassium cyanide, a phase transfer catalyst may be included in thereaction. Particularly suitable phase transfer catalysts are the Crownethers.

A number of different solvents are useful in this process, depending onthe nature of the acid chloride or the acylated product. A preferredsolvent for this reaction is 1,2-dichloroethane. Other solvents whichcan be employed, depending on the reactants or products include toluene,acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, andmethyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanidesource, the rearrangement may be conducted at temperatures up to about50° C.

The above described substituted benzoyl chlorides can be prepared fromthe corresponding substituted benzoic acids according to the teaching ofReagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp.767-769 (1967). ##STR8## wherein R, R⁷ and R⁸ are as previously defined.

The substituted benzoic acids can be prepared by a wide variety ofgeneral methods according to the teaching of The Chemistry of CarboxylicAcids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y.(1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson,J. Wiley and Sons, (1970).

The following are four representative examples of the methods describedtherein. ##STR9## wherein R, R⁷ and R⁸ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux inaqueous sulfuric acid for several hours. The mixture is cooled and thereaction product is isolated by conventional techniques. ##STR10##wherein R, R⁷ and R⁸ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux forseveral hours in an aqueous hypochlorite solution. The mixture is cooledand the reaction product is isolated by conventional techniques.##STR11## wherein R, R⁷ and R⁸ are as defined and X is chlorine, bromineor iodine.

The substituted aromatic halide is allowed to react with magnesium in asolvent such as ether. The solution is then poured over crushed dry iceand the benzoic acid is isolated by conventional techniques.

The following examples teach the synthesis of a representative compoundof this invention.

EXAMPLE I 2-(2-Chloro-4-methanesulfonylbenzoyl)-cyclohexane-1,3-dione##STR12##

1,3-Cyclohexanedione [11.2 grams (g), 0.1 mole] and 23.3 g (0.1 mole)2-chloro-4-methanesulfonylbenzoyl chloride were dissolved in 200 mlmethylene chloride at room temperature. Triethylamine (11 g, 0.11 mole)was slowly added with cooling. The reaction mixture was stirred at roomtemperature for 5 hours and then poured into 2N hydrochloric acid. Theaqueous phase was discarded and the organic phase dried with MgSO₄ andthen evaporated to yield the intermediate enol ester3-(2-chloro-4-methanesulfonylbenzoyloxy)cyclohex-2-enone. The3-(2-chloro-4-methanesulfonylbenzoyloxy)cyclohex-2-enone was dissolvedin 200 ml acetonitrile and triethylamine (22 g, 0.22 mole) was added allat once, followed by acetonecyanohydrin (0.8 g, 0.01 mole). The solutionwas stirred for 5 hours and then poured into 2N HCl and extracted twicewith ethyl acetate. The organic layer was dried with MgSO₄ and thesolvent evaporated to yield the product.

EXAMPLE II3-Chloro-2-(2-chloro-4-methanesulfonylbenzoyl)-cyclohex-2-enone##STR13##

2-(2-Chloro-4-methanesulfonylbenzoyl)-cyclohexane-1,3-dione (9.8 g, 30millimole) was dissolved in 100 ml methylene chloride and stirred atroom temperature. To this solution was added oxalyl chloride (5.7 g, 45mmol) followed by dimethylformamide (0.5 ml) in portions small enough tocontrol effervescence. The resulting solution was stirred for 4 hoursand then poured into water and extracted with methylene chloride. Theorganic layer was washed again with water, saturated K₂ CO₃ solution andthen dried with MgSO₄ and the solvent evaporated to yield3-chloro-2-(2chloro-4-methanesulfonylbenzoyl)cyclohex-2-enone (7.3 g,70%) as an oil which was used without further purification.

EXAMPLE III3-Thioethyl-2-(2-chloro-4-methanesulfonylbenzoyl)-cyclohex-2-enone##STR14##

3-Chloro-2-(2-chloro-4-methanesulfonylbenzoyl)cyclohex-2-enone (4.2 g,12 mmole) was dissolved in 80 ml THF and ethane thiol (0.75 g, 12 mmole)and triethylamine (1.2 g, 12 mmol) were added and the solution stirredfor 18 hours. The reaction mixture was poured into water and extractedwith ethyl acetate. The organic layer was washed with 1N HCl, 1N NaOH,water, dried with MgSO₄ and then evaporated to yield 2.9 g (65%) of arust colored solid, m.p. 151-°154° C.

EXAMPLE IV ##STR15##3-Ethanesulfonyl-2-(2-chloro-4-methanesulfonylbenzoyl)cyclohex2-enone

3-Thioethyl-2-(2-chloro-4-methanesulfonylbenzoyl)-cyclohex-2-enone (2.0g, 5.4 mmol) was dissolved in 50 ml methylene chloride and cooled to 0°C. m-Chloroperoxybenzoic acid (2.2 g, 10 mmol @80%) was addedportion-wise and then stirred for several hours. When TLC showed thereaction was complete, the reaction mixture was transferred to aseparatory funnel, more CH₂ Cl₂ was added and the mixture shaken withNa₂ S₂ O₅ solution, and then 5% K₂ CO₃. The organic layer was dried withMgSO₄ and the solvent evaporated to afford 1.1 g of a solid, m.p.157°-161° C.

The following is a table of certain selected compounds that arepreparable according to the procedure described herein. Compound numbersare assigned to each compound and are used throughout the remainder ofthe application.

                                      TABLE I                                     __________________________________________________________________________     ##STR16##                                                                    Cmpd.                                                                         No. R  R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         R.sup.7                                                                            R.sup.8                                                                             m R.sup.9   m.p. °C.                   __________________________________________________________________________     1  Cl H  H  H H H H 3-Cl 4-Cl  0 C.sub.2 H.sub.5 OC(O)CH.sub.2                                                           55-58                              2  Cl H  H  H H H H 3-Cl 4-Cl  0 phenyl    oil                                3  Cl H  H  H H H H H    4-Cl  0 CH.sub.3  oil                                4  Cl H  H  H H H H H    4-Cl  2 CH.sub.3  oil                                5  NO.sub.2                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H H H H H    H     2 C.sub.2 H.sub.5                                                                         142-147                            6.sup.(a)                                                                        Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                 2 C.sub.2 H.sub.5                                                                         157-161                            7  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                 2 CH.sub.3  81-86                              8  NO.sub.2                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H H H H H    H     0 CH.sub.3 OC(O)CH.sub.2                       9  Cl H  H  H H H H H    4-Cl  0 CH.sub.3 OC(O)CH.sub.2                                                                  oil                               10  Cl H  H  H H H H 3-Cl 4-Cl  0 CH.sub.3 OC(O)CH.sub.2                                                                  oil                               11  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                 O CH.sub.3 OC(O)CH.sub.2                                                                  oil                               12  NO.sub.2                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H H H H H    H     2 CH.sub.3                                    13  NO.sub.2                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H H H H H    H     2 CH.sub.3 OC(O)CH.sub.2                                                                  119-124                           14  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                 0 CN        123-126                           15  NO.sub.2                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H H H H H    H     0 2,3-dichlorophenyl                                                                      121-125                           16  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                 0 4-methoxyphenyl                                                                         oil                               17  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                 0 phenyl    186-188                           18  Cl H  H  H H H H H    4-Cl  0 phenyl    oil                               19  Cl H  H  H H H H H    4-Cl  2 phenyl    oil                               20  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                 0 3-methylphenyl                                                                          oil                               21  NO.sub.2                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H H H H H    H     0 phenyl    152-156                           23  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                 0 2,3-dichlorophenyl                                                                      165-169                           24  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                 2 3-methylphenyl                                                                          oil                               25  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                 2 4-methoxyphenyl                                                                          99-109                           26  Cl H  H  H H H H H    4-Cl  0 3-methylphenyl                                                                          oil                               27  NO.sub.2                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H H H H H    H     2 2,3-dichlorophenyl                                                                      75-76                             28  NO.sub.2                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H H H H H    H     2 phenyl    oil                               29  Cl H  H  H H H H 3-OC.sub.2 H.sub.5                                                                 4-SO.sub.2 C.sub.2 H.sub.5                                                          0 CH.sub.3  oil                               30  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                 1 2,3-dichlorophenyl                                                                       97-102                           31  NO.sub.2                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H H H H H    H     1 3-methylphenyl                                                                          oil                               32  Cl H  H  H H H H H    4-Cl  2 2,3-dichlorophenyl                                                                      161-164                           33  Cl H  H  H H H H 3-Cl 4-Cl  0 3-methylphenyl                                                                          oil                               34  Cl H  H  H H H H 3-Cl 4-Cl  0 phenyl    oil                               35  Cl H  H  H H H H H    4-Cl  0 4-methoxyphenyl                                                                         oil                               36  Cl H  H  H H H H H    4-Cl  2 4-methoxyphenyl                                                                         oil                               37  Cl H  H  H H H H 3-Cl 4-Cl  2 phenyl    69-74                             38  Cl H  H  H H H H 3-C.sub.2 H.sub.5 O                                                                4-SO.sub.2 C.sub.2 H.sub.5                                                          2 CH.sub.3  60-63                             __________________________________________________________________________     .sup.(a) = Prepared in Example IV.                                       

Herbicidal Screening Tests

As previously mentioned, the herein described compounds produced in theabove-described manner are phytotoxic compounds which are useful andvaluable in controlling various plant species. Selected compounds ofthis invention were tested as herbicides in the following manner.

Pre-emergence herbicide test

On the day preceding treatment, seeds of seven different weed speciesare planted in loamy sand soil in individual rows using one species perrow across the width of a flat. The weeds used are green foxtail (FT)(Setaria viridis), watergrass (WG) (Echinochloa crusgalli), wild oat(WO) (Avena fatua), annual morningglory (AMG) (Ipomoea lacunosa),velvetleaf (VL) (Abutilon theophrasti), Indian mustard (MD) (Brassicajuncea) and yellow nutsedge (YNS) (Cyperus esculentus). Ample seeds areplanted to give about 20 to 40 seedlings per row, after emergence,depending upon the size of the plants.

Using an analytical balance, 600 milligrams (mg) of the compound to betested are weighed out on a piece of glassine weighing paper. The paperand compound are placed in a 60 milliliter (ml) wide-mouth clear bottleand dissolved in 45 ml of acetone or substituted solvent. Eighteen ml ofthis solution are transferred to a 60 ml wide-mouth clear bottle anddiluted with 22 ml of a water and acetone mixture (19:1) containingenough polyoxyethylene sorbitan monolaurate emulsifier to give a finalsolution of 0.5% (v/v). The solution is then sprayed on a seeded flat ona linear spray table calibrated to deliver 80 gallons per acre (748L/ha). The application rate is 4 lb/acre (4.48 Kg/ha).

After treatment, the flats are placed in the greenhouse at a temperatureof 70° to 80° F. and watered by sprinkling. Two weeks after treatment,the degree of injury or control is determined by comparison withuntreated check plants of the same age. The injury rating from 0 to 100%is recorded for each species as percent control with 0% representing noinjury and 100% representing complete control.

The results of the tests are shown in the following Table II.

                  TABLE II                                                        ______________________________________                                        Pre-Emergence Herbicidal Activity                                             Application Rate -- 4.48 kg/ha                                                Cmpd.                                                                         No.    FT      WG     WO    AMG   VL    MD   YNS                              ______________________________________                                         1     0       0      0     0     0     0    0                                 2     15      45     0     0     50    30   0                                 3     60      40     0     0     50    50   40                                4     98      100    0     40    100   100  80                                5     100     85     100   20    100   100  80                                6     100     100    90    100   100   100  80                                7     100     100    90    95    100   100  80                                8     100     100    70    30    100   90   70                                9     0       10     0     5     100   100  10                               10     0       10     0     0     100   100  70                               11     0       0      0     0     0     0    0                                12     100     100    70    10    100   95   80                               13     98      98     50    90    100   80   70                               14     50      100    0     25    100   100  80                               15     0       0      10    0     0     0    0                                16     0       10     80    95    100   80   80                               17     10      5      90    100   95    80   80                               18     0       0      0     0     0     0    0                                19     80      5      90    100   100   50   80                               20     0       0      80    50    90    10   80                               21     0       0      0     0     0     0    0                                22     0       0      0     0     0     0    0                                23                                                                            24     100     30     100   100   100   40   80                               25     85      10     100   100   90    50   80                               26     0       0      20    20    0     0    10                               27     100     95     100   95    100   30   80                               28     100     95     100   90    100   10   80                               29     100     80     100   100   100   90   80                               30     100     80     100   100   100   80   80                               31     100     100    100   100   100   20   80                               32     0       0      10    10    0     0    30                               33     50      0      10    10    0     0    0                                34     0       0      10    0     0     0    0                                35     50      0      80    100   100   0    80                               36     0       0      70    100   100   5    80                               37     0       0      30    100   90    5    0                                38     100     100    100   100   100   100  80                               ______________________________________                                    

Post-Emergence Herbicide Test

This test is conducted in an identical manner to the testing procedurefor the pre-emergence herbicide test, except the seeds of the sevendifferent weed species are planted 10-12 days before treatment. Also,watering of the treated flats is confined to the soil surface and not tothe foliage of the sprouted plants.

The results of the post-emergence herbicide test are reported in TableIII.

                  TABLE III                                                       ______________________________________                                        Post-Emergence Herbicidal Activity                                            Application Rate -- 4.48 kg/ha                                                Cmpd.                                                                         No.    FT      WG     WO    AMG   VL    MD   YNS                              ______________________________________                                         1     40      60     10    15    60    60   50                                2     10      50     0     30    90    100  0                                 3     60      40     0     0     50    50   40                                4     0       40     0     40    80    50   5                                 5     75      70     70    60    60    40   80                                6     100     100    95    100   100   100  80                                7     90      85     95    80    95    95   60                                8     98      80     80    60    80    75   70                                9     90      100    90    80    100   85   10                               10     85      95     0     70    100   90   10                               11     0       0      0     0     0     0    0                                12     90      60     50    40    80    60   80                               13     90      80     80    40    100   90   70                               14     10      50     10    40    80    70   10                               15     80      20     80    20    90    20   5                                16     90      80     100   90    100   100  80                               17     30      30     100   90    100   100  60                               18     10      0      90    80    100   100  5                                19     70      5      100   100   100   100  80                               20     5       10     95    100   100   100  70                               21     0       20     60    20    80    20   0                                22     10      20     70    50    50    20   0                                23                                                                            24     95      85     90    100   100   85   80                               25     100     80     100   100   100   100  80                               26     10      0      90    100   100   75   30                               27     90      80     80    80    90    75   80                               28     90      80     85    80    100   50   80                               29     100     70     100   90    90    90   80                               30     100     90     95    100   100   90   80                               31     100     90     90    100   100   80   80                               32     0       0      80    100   100   50   70                               33     0       0      20    80    100   50   10                               34     0       0      50    100   100   40   5                                35     10      0      85    100   100   100  30                               36     0       0      70    100   90    20   30                               37     0       0      30    80    80    50   10                               38     80      50     50    80    70    20   80                               ______________________________________                                    

The compounds of the present invention are useful as herbicides and canbe applied in a variety of ways at various concentrations. In practice,the compounds herein defined are formulated into herbicidalcompositions, by admixture, in herbicidally effective amounts, with theadjuvants and carriers normally employed for facilitating the dispersionof active ingredients for agricultural applications, recognizing thefact that the formulation and mode of application of a toxicant mayaffect the activity of the materials in a given application. Thus, theseactive herbicidal compounds may be formulated as granules of relativelylarge particle size, as wettable powders, as emulsifiable concentrates,as powdery dusts, as flowables, as solutions or as any of several otherknown types of formulations, depending upon the desired mode ofapplication. These formulations may contain as little as about 0.5% toas much as about 95% or more by weight of active ingredient. Aherbicidally effective amount depends upon the nature of the seeds orplants to be controlled and the rate of application varies from about0.01 to approximately 10 pounds per acre, preferably from about 0.02 toabout 4 pounds per acre.

Wettable powders are in the form of finely divided particles whichdisperse readily in water or other dispersants. The wettable powder isultimately applied to the soil either as a dry dust or as a dispersionin water or other liquid. Typical carriers for wettable powders includefuller's earth, kaolin clays, silicas and other readily wet organic orinorganic diluents. Wettable powders normally are prepared to containabout 5% to about 95% of the active ingredient and usually also containa small amount of wetting, dispersing, or emulsifying agent tofacilitate wetting and dispersion.

Emulsifiable concentrates are homogeneous liquid compositions which aredispersible in water or other dispersant, and may consist entirely ofthe active compound with a liquid or solid emulsifying agent, or mayalso contain a liquid carrier, such as xylene, heavy aromatic naphthal,isophorone and other non-volatile organic solvents. For herbicidalapplication, these concentrates are dispersed in water or other liquidcarrier and normally applied as a spray to the area to be treated. Thepercentage by weight of the essential active ingredient may varyaccording to the manner in which the composition is to be applied, butin comprises about 0.5% to 95% of active ingredient by weight of theherbicidal composition.

Granular formulations wherein the toxicant is carried on relativelycoarse particles, are usually applied without dilution to the area inwhich suppression of vegetation is desired. Typical carriers forgranular formulations include sand, fuller's earth, attapulgite clay,bentonite clays, montmorillonite clay, vermiculite, perlite and otherorganic or inorganic materials which absorb or which may be coated withthe toxicant. Granular formulations normally are prepared to containabout 5% to about 25% of active ingredients which may includesurface-active agents such heavy aromatic naphthas, kerosene or otherpetroleum fractions, or vegetable oils; and/or stickers such asdestrins, glue or synthetic resins.

Typical wetting, dispersing or emulsifying agents used in agriculturalformulations include, for example, the alkyl and alkylaryl sulfonatesand sulfates and their salts; polyhydric alcohols; polyethoxylatedalcohols; esters and fatty amines; and other types of surface-activeagents, many of which are available in commerce. The surface-activeagent, when used, normally comprises from 0.1% to 15% by weight of theherbicidal composition.

Dusts, which are free-flowing admixtures of the active ingredient withfinely divided solids such as talc, clays, flours and other organic andinorganic solids which act as dispersants and carriers for the toxicant,are useful formulations for soil-incorporating application.

Pastes, which are homogeneous suspensions of a finely divided solidtoxicant in a liquid carrier such as water or oil, are employed forspecific purposes. These formulations normally contain about 5% to about95% of active ingredient by weight, and may also contain small amountsof a wetting, dispersing or emulsifying agent to facilitate dispersion.For application, the pastes are normally diluted and applied as a sprayto the area to be affected.

Other useful formulations for herbicidal applications include simplesolutions of the active ingredient in a dispersant in which it iscompletely soluble at the desired concentration, such as acetone,alkylated napthalenes, xylene and other organic solvents. Pressurizedsprays, typically aerosols, wherein the active ingredient is dispersedin finely-divided form as a result of vaporization of a low boilingdispersant solvent carrier, such as the Freons, may also be used.

The phytotoxic compositions of this invention can be applied to theplants in the conventional manner. Thus, the dust and liquidcompositions can be applied to the plant by the use of power-dusters,boom and hand sprayers and spray dusters. The compositions can also beapplied from airplanes as a dust or a spray or by rope wick applicationsbecause they are effective in very low dosages. In order to modify orcontrol growth of germinating seeds or emerging seedlings, as a typicalexample, the dust and liquid compositions can be applied to the soilaccording to conventional methods and can be distributed in the soil toa depth of at least 1/2 inch below the soil surface. It is not necessarythat the phytotoxic compositions be mechanically admixed with the soilparticles since these compositions can also be applied merely byspraying or sprinkling the surface of the soil. The phytotoxiccompositions of this invention can also be applied by addition toirrigation water supplied to the field to be treated. This method ofapplication permits the penetration of the compositions into the soil asthe water is absorbed therein. Dust compositions, granular compositionsor liquid formulations applied to the surface of the soil can bedistributed below the surface of the soil by conventional means such asdiscing, dragging or mixing operations.

    ______________________________________                                        EMULSIFIABLE CONCENTRATE FORMULATIONS                                         General Formula                                                               with Ranges     Specific Formula                                              ______________________________________                                        Herbicidal                                                                               5-55     herbicidal compound                                                                           24                                        compound            proprietary blend of oil-                                                                     10                                        surfactant(s)                                                                            5-25     soluble sulfonates and -solvent(s)                                                            20-90 polyoxyethylene ethers                        100%      polar solvent   27                                                            petroleum hydrocarbon                                                                         39                                                                            100%                                      WETTABLE POWDER FORMULATIONS                                                  herbicidal                                                                               3-90     herbicidal compound                                                                           80                                        compound            sodium dialkyl  0.5                                       wetting agent                                                                           0.5-2     naphthylene sulfonate                                     dispersing agent                                                                        1-8       sodium lignosulfonate                                                                         7                                         diluent(s)                                                                              8.5-87    attapulgite clay                                                                              12.5                                                100%                      100%                                      EXTRUDED GRANULAR FORMULATIONS                                                herbicidal                                                                               1-20     herbicidal compound                                                                           10                                        compound            lignin sulfonate                                                                              5                                         binding agent                                                                            0-10     calcium carbonate                                                                             85                                        diluent(s)                                                                              70-99                      100%                                               100%                                                                FLOWABLE FORMULATIONS                                                         herbicidal                                                                              20-70     herbicidal compound                                                                           45                                        compound            polyoxyethylene ether                                                                         5                                         surfactant(s)                                                                            1-10     attagel         0.05                                      suspending                                                                              0.05-1    propylene glycol                                                                              10                                        agent(s)            1,2-benzisothiazoline-                                                                        0.03                                      antifreeze agent                                                                         1-10     3-one                                                     antimicrobial                                                                            1-10     silicone defoamer                                                                             0.02                                      agent               water           39.9                                      antifoam agent                                                                          0.1-1                     100%                                      solvent    7.95-77.85                                                                   100%                                                                ______________________________________                                    

The phytotoxic compositions of this invention can also contain otheradditives, for example, fertilizers, other herbicides and otherpesticides, used as adjuvant or in combination with any of theabove-described adjuvants. Fertilizers useful in combination with theactive ingredients include, for example, ammonium nitrate, urea andsuperphosphate.

What is claimed is:
 1. A compound of the formula ##STR17## wherein R ishalogen, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, nitro; cyano; C₁ -C₂ haloalkyl, orR^(a) SO_(n) -- wherein n is 0 or 2 and R^(a) is C₁ -C₂ alkyl;R¹ ishydrogen or C₁ -C₄ alkyl; R² is hydrogen or C₁ -C₄ alkyl; or R¹ and R²together are alkylene having 2 to 5 carbon atoms; R³ is hydrogen or C₁-C₄ alkyl; R⁴ is hydrogen or C₁ -C₄ alkyl; or R³ and R⁴ together can beoxo; R⁵ is hydrogen or C₁ -C₄ alkyl; R⁶ is hydrogen or C₁ -C₄ alkyl; orR⁵ and R⁶ together are alkylene having 2 to 5 carbon atoms; R⁷ and R⁸independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁-C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2; andR^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen orcyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) andR^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)--wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) SO₂ NR^(c) R^(d)wherein R^(c) and R^(d) are as defined; or (13) --N(R^(c))C(O)R^(d)wherein R^(c) and R^(d) are as defined; m is the integer 0, 1 or 2; andR⁹ is C₁ -C₄ alkyl; phenyl; dichlorophenyl; methylphenyl; methoxyphenyl;cyano; or --(CH₂)_(x) C(O)O--(C₁ -C₄ alkyl) wherein X is the integer 1,2, or
 3. 2. The compounds of claim 1 wherein R is chlorine, bromine, C₁-C₂ alkyl, C₁ -C₂ alkoxy, cyano, nitro, C₁ -C₂ alkylthio or C₁ -C₂ alkylsulfonyl; R¹ is hydrogen or methyl; R² is hydrogen or methyl; R³ ishydrogen or methyl; R⁴ is hydrogen or methyl; R⁵ is hydrogen or methyl;R⁶ is hydrogen or methyl; R⁷ and R⁸ independently are (1) hydrogen; (2)halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6)cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n isthe integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkylsubstituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10)--NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁-C₄ alkyl; (11) R^(e) C(O)-- wherein R³ is C₁ -C₄ alkyl or C₁ -C₄alkoxy; (12) SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or(13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined; m isthe integer 0, 1 or 2; and R⁹ is methyl, ethyl, phenyl, CH₃ OC(O)CH₂ --,C₂ H₅ OC(O)CH₂ --, dichlorophenyl, methylphenyl, methoxyphenyl or cyano.3. The compounds of claim 2 wherein R⁷ and R⁸ are independently arehydrogen; chlorine; fluorine; bromine; methyl; methoxy;trifluoromethoxy; cyano; nitro; trifluoromethyl; R^(b) SO_(n) -- whereinn is the integer 2 and R^(b) is methyl, chloromethyl, trifluoromethyl,cyanomethyl, ethyl, or n-propyl; --NR^(c) R^(d) wherein R^(c) and R^(d)independently are hydrogen or C₁ -C₄ alkyl; R^(e) C(O)-- where R^(e) isC₁ -C₄ alkyl or C₁ -C₄ alkoxy or SO₂ NR^(c) R^(d) wherein R^(c) andR^(d) are as defined and R⁷ is in the 3-position, and R⁸ is in the4-position.
 4. The compound of claim 2 wherein R⁷ is hydrogen, R⁸ ishydrogen, chlorine, bromine, fluorine, trifluoromethyl or R^(b) SO₂wherein R^(b) is C₁ -C₄ alkyl and R⁹ is methyl, ethyl or phenyl.
 5. Thecompound of claim 2 wherein R is chlorine; R¹ is hydrogen; R² ishydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ ishydrogen; R⁷ is hydrogen; R⁸ is 4--CH₃ SO₂ ; R⁹ is ethyl; and m is
 2. 6.The compound of claim 2 wherein R is chlorine; R¹ is hydrogen; R² ishydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ ishydrogen; R⁷ is hydrogen; R⁸ is 4--CH₃ SO₂ --; R⁹ is methyl; and m is 2.7. The compound of claim 2 wherein R is nitro; R¹ is methyl; R² ismethyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen;R⁷ is hydrogen; R⁸ is hydrogen; R⁹ is phenyl; and m is
 0. 8. Thecompound of claim 2 wherein R is chlorine; R¹ is hydrogen; R² ishydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ ishydrogen; R⁷ is hydrogen; R⁸ is 4--CH₃ SO₂ --; R⁹ is 2,3-dichlorophenyl;and m is
 1. 9. The compound of claim 2 wherein R is nitro; R¹ is methyl;R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ ishydrogen; R⁷ is hydrogen; R⁸ is hydrogen; R⁹ is 3-methylphenyl and mis
 1. 10. The compound of claim 2 wherein R is chlorine; R¹ is hydrogen;R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ ishydrogen; R⁷ is 3-ethoxy; R⁸ is 4--C₂ H₅ SO₂ --; R⁹ is methyl; and m is2.
 11. An herbicidal composition comprising an herbicidally effectiveamount of a 3-substituted thio-2-benzoyl-cyclohex-2-enone compound ofthe formula ##STR18## wherein R is halogen, C₁ -C₂ alkyl, C₁ -C₂ alkoxy,nitro; cyano; C₁ -C₂ haloalkyl, or R^(a) SO_(n) -- wherein n is 0 or 2and R^(a) is C₁ -C₂ alkyl;R¹ is hydrogen or C₁ -C₄ alkyl; R² is hydrogenor C₁ -C₄ alkyl; or R¹ and R² together are alkylene having 2 to 5 carbonatoms; R³ is hydrogen or C₁ -C₄ alkyl; R⁴ is hydrogen or C₁ -C₄ alkyl;or R³ and R⁴ together can be oxo; R⁵ is hydrogen or C₁ -C₄ alkyl; R⁶ ishydrogen or C₁ -C₄ alkyl; or R⁵ and R⁶ together are alkylene having 2 to5 carbon atoms; R⁷ and R⁸ independently are (1) hydrogen; (2) halogen;(3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano;(7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is theinteger 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkylsubstituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10)--NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁-C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄alkoxy; (12) SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or(13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined; m isthe integer 0, 1 or 2; and R⁹ is C₁ -C₄ alkyl; phenyl; dichlorophenyl;methylphenyl; methoxyphenyl; cyano; or --(CH₂)xC(O)O--(C₁ -C₄ alkyl)wherein X is the integer 1, 2, or 3 and an inert carrier therefor. 12.The composition of claim 11 wherein R is chlorine, bromine, C₁ -C₂alkyl, C₁ -C₂ alkoxy, cyano, nitro, C₁ -C₂ alkylthio or C₁ -C₂alkylsulfonyl; R¹ is hydrogen or methyl; R² is hydrogen or methyl; R³ ishydrogen or methyl; R⁴ is hydrogen or methyl; R⁵ is hydrogen or methyl;R⁶ is hydrogen or methyl; R⁷ and R⁸ independently are (1) hydrogen; (2)halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6)cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n isthe integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkylsubstituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10)--NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁-C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄alkoxy; (12) SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or(13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined; m isthe integer 0, 1 or 2; and R⁹ is methyl, ethyl, phenyl, CH₃ OC(O)CH₂ --,C₂ H₅ OC(O)CH₂ --, dichlorophenyl, methylphenyl, methoxyphenyl or cyano.13. The composition of claim 11 wherein R⁷ and R⁸ are independently arehydrogen; chlorine; fluorine; bromine; methyl; methoxy;trifluoromethoxy; cyano; nitro; trifluoromethyl; R^(b) SO_(n) -- whereinn is the integer 2 and R^(b) is methyl, chloromethyl, trifluoromethyl,cyanomethyl, ethyl, or n-propyl; --NR^(c) R^(d) wherein R^(c) and R^(d)independently are hydrogen or C₁ -C₄ alkyl; R^(e) C(O)-- where R^(e) isC₁ -C₄ alkyl or C₁ -C₄ alkoxy or SO₂ NR^(c) R^(d) wherein R^(c) andR^(d) are as defined and R⁷ is in the 3-position, and R⁸ is in the4-position.
 14. The composition of claim 11 wherein R⁷ is hydrogen, R⁸is hydrogen; chlorine; bromine; fluorine; trifluoromethyl; or R² SO₂wherein R^(b) is C₁ -C₄ alkyl; and R⁹ is methyl, ethyl or phenyl. 15.The composition of claim 11 wherein R is chlorine; R¹ is hydrogen; R² ishydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ ishydrogen; R⁷ is hydrogen; R⁸ is 4--CH₃ SO₂ ; R⁹ is ethyl; and m is 2.16. The composition of claim 11 wherein R is chlorine; R¹ is hydrogen;R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ ishydrogen; R⁷ is hydrogen; R⁸ is 4--CH₃ SO₂ --; R⁹ is methyl; and m is 2.17. The composition of claim 11 wherein R is nitro; R¹ is methyl; R² ismethyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen;R⁷ is hydrogen; R⁸ is hydrogen; R⁹ is phenyl; and m is
 0. 18. Thecomposition of claim 11 wherein R is chlorine; R¹ is hydrogen; R² ishydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ ishydrogen; R⁷ is hydrogen; R⁸ is 4--CH₃ SO₂ --; R⁹ is 2,3-dichlorophenyl;and m is
 1. 19. The composition of claim 11 wherein R is nitro; R¹ ismethyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶is hydrogen; R⁷ is hydrogen; R⁸ is hydrogen; R⁹ is 3-methylphenyl and mis
 1. 20. The composition of claim 11 wherein R is chlorine; R¹ ishydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ ishydrogen; R⁶ is hydrogen; R⁷ is 3-ethoxy; R⁸ is 4--C₂ H₅ SO₂ --; R⁹ ismethyl; and m is 2.